Fabric rinse composition containing a benztriazole uv absorber

ABSTRACT

Disclosed is a fabric rinse composition comprising a) 0.1 to 10% by weight of a UV absorber of formula(1), wherein A is a radical of formula (1 a ); B is a radical of formula (1 c ); (1 d ); (1 e ); (1 f ), (1 g ); (1 h ); (1 i ); (1 k ); (1 l ); or (1 m ); R1, R2, R3, R4, R5 and R6 are each independently of the others hydrogen, C1-C18alkyl; C5-C7-cycloalkyl; halogen; R9 is hydrogen, C1-C12alkyl; or C5-C7cycloalkyl; R7, R8 and R10 are each independently of the others hydrogen, C1-C12alkyl, C5-C7cycloalkyl, C1-C12hydroxyalkyl; X is halogen; a radical of formula (1 s ); or (1 u ); sulfate, phosphate, lactate, citrate, tartrate; R11 is C1-C12alkyl; C5-C7cycloalkyl or phenyl: x is from 0 to 10; and y is from 1 to 20; b) 5 to 25% by weight, based on the total weight of the composition of a fabric softener agent; and c) the remainder being substantially water.

[0001] The present invention relates to a fabric rinse compositioncontaining a benztriazole UV absorber; and to a method of treatingtextiles with the composition, which method imparts to textile fibermaterial so treated, in addition to an excellent UV Protecting Factor(UPF) value, and other desirable properties.

[0002] It is known that light radiation of wavelengths 280-400 nmpermits tanning of the epidermis. Also known is that rays of wavelengths280-320 nm (termed UV-B radiation), cause erythemas and skin burningwhich can inhibit skin tanning.

[0003] Radiation of wavelengths 320-400 nm (termed UV-A radiation) isknown to induce skin tanning but can also cause skin damage, especiallyto sensitive skin which is exposed to sunlight for long periods.Examples of such damage include loss of skin elasticity and theappearance of wrinkles, promotion of the onset of erythemal reaction andthe inducement of phototoxic or photoallergic reactions.

[0004] Any effective protection of the skin from the damaging effects ofundue exposure to sunlight clearly needs to include means for absorbingboth UV-A and UV-B components of sunlight before they reach the skinsurface.

[0005] Traditionally, protection of exposed human skin against potentialdamage by the UV components in sunlight has been effected by directlyapplying to the skin a preparation containing a UV absorber.

[0006] One aspect of the desire to increase the level of skin protectionagainst sunlight has been the consideration of additional measures, overand above the direct protection of the skin. For example, considerationhas been given to the provision of protection to skin covered byclothing and thus not directly exposed to sunlight.

[0007] Most natural and synthetic textile materials are at leastpartially permeable to UV components of sunlight. Accordingly, the merewearing of clothing does not necessarily provide skin beneath theclothing with adequate protection against damage by UV radiation.Although clothing containing a deeply colored dye and/or having a tightweave texture may provide a reasonable level of protection to skinbeneath it, such clothing is not practical in hot sunny climates, fromthe standpoint of the personal comfort of the wearer.

[0008] There is a need, therefore, to provide protection against UVradiation for skin which lies underneath clothing, including lightweightsummer clothing, which is undyed or dyed only in pale shades. Dependingon the nature of the dyestuff, even skin beneath clothing dyed in somedark shades may also require protection from UV radiation.

[0009] Such lightweight summer clothing normally has a density of lessthan 200 g/m² and has a sun protection factor rating between 1.5 and 20,depending on the type of fibre from which the clothing is manufactured.

[0010] The UPF rating of a sun protectant (sun cream or clothing) may bedefined as the multiple of the time taken for the average person wearingthe sun protectant to suffer sun burning under average exposure to sun.For example, if an average person would normally suffer sun burn after30 minutes under standard exposure conditions, a sun protectant havingan UPF rating of 5 would extend the period of protection from 30 minutesto 2 hours and 30 minutes. For people living in especially sunnyclimates, where mean sun burn times are minimal, e.g. only 15 minutesfor an average fair-skinned person at the hottest time of the day, UPFratings of about 20 are desired for lightweight clothing.

[0011] The selection of a suitable UVA, for use in a method foreffecting an increase in the UPF value of a textile fiber material(often referred to as a “UV cutting” treatment method), has to take intoaccount the fact that the treated textile fiber material must satisfyperformance criteria in a wide range of areas, such as washfastness,lightfastness and tear resistance, apart from its UPF value.

[0012] Another major problem for consumers in many parts of the world isthe fading of colored fabrics by sunlight (so-called “photo-fading”)during wear and during drying. Thus susceptible fabrics in temperatureand high latitude regions in addition to those in the tropics can beseverely faded. Photo- fading of fabrics is of specific concern toconsumers because the contrast between exposed and unexposed areas makesit particularly noticeable.

[0013] Surprisingly it was found that the use of specific UV absorbersin a fabric rinse composition imparts enhanced UPF, and simultaneouslyeffectively prevents the photo-fading of said fabric.

[0014] Therefore the present invention provides a stable, concentratedfabric rinse composition comprising

[0015] fabric rinse composition comprising

[0016] a) 0.1 to 10, preferably 0.1 to 5% by weight of a UV absorber offormula

[0017] wherein

[0018] A is a radical of formula

[0019] or

[0020] B is a radical of formula

[0021] R₁, R₂, R₃, R₄, R₅ and R₆ are each independently of the othershydrogen, C₁-C₁₈alkyl; C₅-C₇-cycloalkyl; halogen;

[0022] R₉ is hydrogen, C₁-C₁₂alkyl; or C₅-C₇cycloalkyl;

[0023] R₇, R₈ and R₁₀ are each independently of the others hydrogen,C₁-C₁₂alkyl, C₅-C₇cycloalkyl, C₁-C₁₂hydroxyalkyl;

[0024] X is halogen; a radical of formula

[0025] sulfate, phosphate, lactate, citrate, tartrate;

[0026] R₁₁ is C₁-C₁₂alkyl; C₅-C₇cycloalkyl or phenyl;

[0027] x is from 0 to 10; and

[0028] y is from 1 to 20;

[0029] b) 5 to 25% by weight, based on the total weight of thecomposition of a fabric softener agent; and

[0030] c) the remainder being substantially water.

[0031] The invention preferably relates to the use of a composition,wherein component (a) corresponds to the compounds of formulae

[0032] wherein

[0033] R₁, R₂, R₃, R₄, R₅, R₆ and A are as defined for formula (1).

[0034] According to the invention there are preferably used as component(a) compounds of formulae (1), (2) and (3) wherein

[0035] A is a radical of formula

[0036] wherein

[0037] B is a radical of formula (1c); or (1d);and

[0038] x and y are as defined for formula (1).

[0039] Special preference is given to compounds of formulae (1), (2) and(3) wherein

[0040] R₉ is hydrogen; or C₁-C₅alkyl.

[0041] The following benzotriazole UV absorbers used according to theinvention may be mentioned by way of example:

[0042] The UV absorber used in the present composition readily absorbsUV light, especially in the range I=300 to 400 nm, and converts theabsorbed energy, by a chemical intermediate reaction, intonon-interfering, stable compounds or into non-interfering forms ofenergy. The UV absorber should, of course, be compatible with the rinsecycle fabric softener composition. Preferably, the UV absorber used isone which is capable of being absorbed on to the washed textile articleduring a rinse cycle fabric softener treatment.

[0043] Fabric softeners (component (b)) suitable for use herein areselected from the following classes of compounds:

[0044] (i) Cationic quaternary ammonium salts. The counter ion of suchcationic quaternary ammonium salts may be a halide, such as chloride orbromide, methyl sulfate, or other ions well known in the literature.Preferably the counter ion is methyl sulfate or any alkyl sulfate or anyhalide, methyl sulfate being most preferred for the dryer-added articlesof the invention.

[0045] Examples of cationic quaternary ammonium salts include but arenot limited to:

[0046] 1. Acyclic quaternary ammonium salts having at least two C₈ toC₃₀, preferably C₁₂ to C₂₂ alkyl or alkenyl chains, such as:ditallowdimethyl ammonium methylsulfate, di(hydrogenated tallow)dimethylammonium methylsulfate, distearyldimethyl ammonium methylsulfate orchloride, dicocodimethyl ammonium methylsulfate and the like. It isespecially preferred if the fabric softening compound is a waterinsoluble quaternary ammonium material which comprises a compound havingtwo C₁₂ to C₁₈ alkyl or alkenyl groups connected to the molecule via atleast one ester link. It is more preferred if the quaternary ammoniummaterial has two ester links present. An especially preferredester-linked quaternary ammonium material for use in the invention canbe represented by the formula:

[0047] wherein each R₁₂ group is independently selected from C₁ to C₄alkyl, hydroxyalkyl or C₂ to C₄ alkenyl groups; T is either

[0048] and wherein each R₁₃ group is independently selected from C₈ toC₂₈ alkyl or alkenyl groups; and e is an integer from 0 to 5.

[0049] A second preferred type of quaternary ammonium material can berepresented by the formula:

[0050] wherein R₄, R₅ and e are as defined in formula (16).

[0051] 2. Cyclic quaternary ammonium salts of the imidazolinium typesuch as di(hydrogenated tallow)dimethyl imidazolinium methylsulfate,1-ethylene-bis(2-tallow-1-methyl) imidazolinium methylsulfate and thelike;

[0052] 3. Diamido quaternary ammonium salts such as:methyl-bis(hydrogenated tallow amidoethyl)-2-hydroxethyl ammonium methylsulfate, methyl bi(tallowamidoethyl)-2-hydroxypropyl ammoniummethylsulfate and the like;

[0053] 4. Biodegradable quaternary ammonium salts such asN,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium methyl sulfate andN,N-di(tallowoyl-oxy-propyl)-N,N-dimethyl ammonium methyl sulfate.Biodegradable quaternary ammonium salts are described, for example, inU.S. Pat. Nos. 4,137,180, 4,767,547 and 4,789,491 incorporated byreference herein.

[0054] Preferred biodegradable quaternary ammonium salts include thebiodegradable cationic diester compounds as described in U.S. Pat. No.4,137,180, herein incorporated by reference.

[0055] (ii) Tertiary fatty amines having at least one and preferably twoC₈-C₃₀, preferably C₁₂-C₂₂ alkyl chains. Examples include hardenedtallow-di-methylamine and cyclic amines such as 1-(hydrogenatedtallow)amidoethyl-2-(hydrogenated tallow) imidazoline. Cyclic amineswhich may be employed for the compositions herein are described in U.S.Pat. No. 4,806,255 incorporated by reference herein.

[0056] (iii) Carboxylic acids having 8 to 30 carbons atoms and onecarboxylic group per molecule. The alkyl portion has 8 to 30, preferably12 to 22 carbon atoms. The alkyl portion may be linear or branched,saturated or unsaturated, with linear saturated alkyl preferred. Stearicacid is a preferred fatty acid for use in the composition herein.Examples of these carboxylic acids are commercial grades of stearic acidand palmitic acid, and mixtures thereof which may contain small amountsof other acids.

[0057] (iv) Esters of polyhydric alcohols such as sorbitan esters orglycerol stearate. Sorbitan esters are the condensation products ofsorbitol or iso-sorbitol with fatty acids such as stearic acid.Preferred sorbitan esters are monoalkyl. A common example of sorbitanester is SPAN 60 (ICI) which is a mixture of sorbitan and isosorbidestearates.

[0058] (v) Fatty alcohols, ethoxylated fatty alcohols, alkyphenols,ethoxylated alkyphenols, ethoxylated fatty amines, ethoxylatedmonoglycerides and ethoxylated diglycerides.

[0059] (vi) Mineral oils, and polyols such as polyethylene glycol.

[0060] These softeners are more definitively described in U.S. Pat. No.4,134,838 the disclosure of which is incorporated by reference herein.Preferred fabric softeners for use herein are acyclic quaternaryammonium salts. Di(hydrogenated)tallowdimethyl ammonium methyl-sulfateis most widely used for dryer articles of this invention. Mixtures ofthe above mentioned fabric softeners may also be used.

[0061] In addition, the composition according to the present inventionmay also contain a minor proportion of one or more adjuvants. Examplesof adjuvants include emulsifiers, perfumes, colouring dyes, opacifiers,fluorescent whitening agents, bactericides, nonionic surfactants,anti-gelling agents such as nitrites or nitrates of alkali metals,especially sodium nitrate, and corrosion inhibitors such as sodiumsilicate.

[0062] The amount of each of these optional adjuvants preferably rangesfrom 0.05 to 5% by weight of the composition.

[0063] A particularly preferred optional adjuvant is a cationic,amphoteric or anionic fluorescent whitening agent as disclosed inEP-A-0,659,877, from page 9 to page 15, line 56.

[0064] The present invention also provides a method for the improvementof UPF of a textile article, comprising applying, to a previously washedarticle, a fabric rinse composition comprising:

[0065] a) 0.1 to 10, preferably 0.1 to 5% by weight of a UV absorber offormula (1), based on the total weight of the composition;

[0066] b) 5 to 25%, especially from 10 to 20% by weight, based on thetotal weight of the composition, of a fabric care ingredient; and

[0067] c) the remainder being substantially water.

[0068] The method and composition of the present invention, in additionto providing protection to the skin, also increase the useful life of atextile article treated according to the present invention, for exampleby preserving its tear strength and/or its lightfastness or reducing thefading from sunlight.

[0069] Therefore the present invention also provides a method for thereducing of the fading of fabrics from sunlight, comprising applying, toa previously washed article, a fabric rinse composition comprising:

[0070] a) 0.1 to 10, preferably 0.1 to 5% by weight of a UV absorber offormula (1), based on the total weight of the composition;

[0071] b) 5 to 25%, especially from 10 to 20% by weight, based on thetotal weight of the composition, of a fabric care ingredient; and

[0072] c) the remainder being substantially water.

[0073] The composition deposit from about 0.5 mg/g fabric to about 5mg/g fabric of the UV absorber of formula (1) onto the fabric to reducethe sun fading of fabric.

[0074] The textile article treated according to the method of thepresent invention may be composed of any of a wide range of types offibers such as wool, polyamide, cotton, polyester, polyacrylic, silk orany mixture thereof.

[0075] Treatment of fabric with compositions of the present inventionrepeatedly during the rinse cycle of a typical laundering process mayresult in higher deposition levels, which contributes even further tothe sun-fading benefit.

[0076] The following Examples further illustrate the present invention.

EXAMPLE 1

[0077] 5 g of bleached cotton fabric (weave) are washed/rinsed in alinitest applying the following conditions:

[0078] Main Wash: Detergent dosage: 4 g/l ECE 77 (phosphate containingstandard detergent which is free of fluorescent whitening and bleachingagents) Liquor ratio: 1:20 Duration: 15 minutes Temperature: 25° C.

[0079] Rinsing is carried out with tap water for 30 seconds and the spindried.

[0080] Rinse Bath: Softener dosage: 1.66 g/l concentrated Esterquat or 5g/l diluted DSDMAC Liquor ration: 1:40 Duration: 15 minutes Temperature:25° C.

[0081] The fabric is spin dried at 60° C.; 1 and 3 wash cycles. TABLE 1Softener formulation: Esterquat DSDMAC formulation formulationDi-(palmcarboxyethyl)- 15% active matter — hydroxyethyl-methylammonium-methosulfate (Rewoquat WE 38 DPG) Distearyl- — 5% active matterdimethylammoniumchloride (Arquad 2 HT-75) C₁₂-C₁₃ fatyy alcoholethoxylate — 0.5% with an average of 6 EO units (Dobanol 23-6, 5) MgCl₂0.1% — UV-Absorber of formulas 2.4% 0.8% (4), (6), (7), (8) and (12)water ad 100% ad 100%

[0082] The UPF of the dried softener treated goods are determined bymeasurement of the UV light transmitted through the textile, using adouble grating spectrophotometer fitted with an Ulbricht bowl.Calculation of UPF is conducted as described by B. L. Diffey and J.Robson in J. Soc. Cosm. Chem. 40 (1989), pp. 130-131.

[0083] The results are shown in Table 2: TABLE 2 softener formulationwithout UV Compound of formula absorber (4) (6) (7) (8) DSDMACformulation 1^(st) wash/rinse 3 13 13 11 11 3^(rd) wash/rinse 3 25 29 2021 Esterquat formulation 1^(st) wash/rinse 3 14 12 10 10 3^(rd)wash/rinse 3 26 25 23 24

[0084] The results in Table 1 and 2 clearly demonstrate the improvementof the UPF values of the cotton substrates treated with rinsecompositions according to the present invention.

EXAMPLE 2

[0085] Photo Fading Inhibition

[0086] Six differently colored cotton fabrics A: Reactive Black 005 B:Reactive Red 226 C: Reactive Blue 013 D: Reactive Red 264 E: ReactiveRed 228

[0087] are separately washed and rinsed in a Linitest applying thefollowing conditions:

[0088] Main Wash: Detergent dosage: 4 g/l ECE77 Liquor Ration: 1:20Duration: 15 minutes Temperature: 25° C.

[0089] The fabrics are rinsed with tap water for 30 seconds and spindried.

[0090] Rinse Bath: Softener dosage: 4 g/l DSDMAC formulation Liquorration: 1:20 Duration: 15 minutes Temperature: 25° C.

[0091] The fabric is spin dried at 60° C. and irradiated in an ATLASWeather-O-Meter Ci65A under the following conditions: Filter: Boro/BoroIrradiation lamp: 3.5 kw Irradiation onto the fabric: 0.22 W/m² Drybulb: 29.3° C. Wet bulb: 21.9° C. Wet bulb depression:  7.3° C. Rel.humidity 43% Duration: 7 h

[0092] 10 wash/rinse/irradiation cycles TABLE 3 Softener formulation:DSDMAC formulation Distearyt-dimethylammoniumchloride — (Arquad 2 HT-75)C₁₂-C₁₃ fatyy alcohol ethoxylate with an 0.5% average of 6 EO units(Dobanol 23-6, 5) UV-Absorber 0.8% of compound of formula (12) water ad100%

[0093] Effect Evaluation CIE Color Measurement

[0094] The CIE color system evaluates the color of a fabric sampel interms of the L*, a*, b* coordinates which are determinded fromspectrophotometer readings. (L*, a*, b* are as described in Colorimetry,2^(nd) Edition, CIE Publication no. 15.2, published by Bureau, Centralde la CIE, Paris 1982).

[0095] The ΔE value is defined by the following equation:

ΔE={(L ₁ *−L ₁*)²+(a ₁ *−a ₁*)²+(b ₁ *−b ₁*)²}^(1/2)

[0096] where the subscripts I and f refer to the values as measured withor without irradiation of the sample, respectively.

[0097] The CIE color measurements of the colored fabric washed/rinsedwithout UV-aborber/irradiated (reference=not irradiated) and the coloredfabric washed/rinsed with UV-absorber/irradiated (reference=notirradiated) obtained the following results: TABLE 4 ΔE 10 Cycles withoutcompound of formula (12) with compound of formula (12) A: 8.9 7.8 B:17.1 15.8 C: 6.2 5.1 D: 13.5 10.9 E: 14.1 11.7

[0098] The results in the table show that the colored cotton fabricstreated according to the process of the present invention show aremarkable photo-fading inhibition.

1. fabric rinse composition comprising a) 0.1 to 10% by weight of a UVabsorber of formula

wherein A is a radical of formula

B is a radical of formula

R₁, R₂, R₃, R₄, R₅, and R₆ are each independently of the othershydrogen, C₁-C₁₈alkyl; C₅-C₇-cycloalkyl; halogen; R₉ is hydrogen,C₁-C₁₂alkyl; or C₅-C₇cycloalkyl; R₇, R₈ and R₁₀ are each independentlyof the others hydrogen, C₁-C₁₂alkyl, C₅-C₇cycloalkyl,C₁-C₁₂hydroxyalkyl; X is halogen; a radical of formula

sulfate, phosphate, lactate, citrate, tartrate; R₁₁ is C₁-C₁₂alkyl;C₅-C₇cycloalkyl or phenyl; x is from 0 to 10; and y is from 1 to 20; b)5 to 25% by weight, based on the total weight of the composition of afabric softener agent; and c) the remainder being substantially water.2. A composition according to claim 1 wherein component (a) correspondsto a UV absorber of formula

wherein R₁, R₂, R₃, R₄, R₅, R₆ and A are as defined in claim
 1. 3. Acomposition according to claim 1 or 2, wherein component (a) correspondsto a UV absorber of formula

wherein R₁, R₂, R₃, R₄, R₅, R₆ and A are as defined in claim
 1. 4. Acomposition according to any one of claims 1 to 3 wherein A is a radicalof formula

or (1b), wherein B is a radical of formula (1c); or (1d); and x and yare as defined in claim
 1. 5. A composition according to any of thepreceding claims in which the fabric care ingredient is selected fromcationic quaternary ammonium salts, tertiary fatty amines having atleast one C₈-C₃₀ alkyl chain, carboxylic acids having 8 to 30 carbonsatoms and one carboxylic group per molecule, esters of polyhydricalcohols, fatty alcohols, ethoxylated fatty alcohols, alkyphenols,ethoxylated alkyphenols, ethoxylated fatty amines, ethoxylatedmonoglycerides and ethoxylated diglycerides, mineral oils and polyols.6. A composition according to claim 5, wherein cationic quaternaryammonium salt fabric softener is selected from acyclic quaternaryammonium salts having at least two C₈ to C₃₀ alkyl or alkenyl chains,cyclic quaternary ammonium salts, diamido quaternary ammonium salts andbiodegradable quaternary ammonium salts.
 7. A composition according toclaim 6, wherein acyclic quaternary ammonium salts correspond to formula

wherein each R₁₂ group is independently selected from C₁ to C₄ alkyl,hydroxyalkyl or C₂ to C₄ alkenyl groups; T is either

and wherein each R₁₃ group is independently selected from C₈ to C₂₈alkyl or alkenyl groups; and e is an integer from 0 to
 5. 8. Acomposition according to claim 7, wherein acyclic quaternary ammoniumsalts correspond to formula

wherein R₄,R₅ and e are as defined in claim
 7. 9. A compositionaccording to claim 7, wherein the acyclic quaternary ammonium salt isdi-(palmcarboxyethyl)-hydroxyethyl-methylammonium-methosulfate.
 10. Acomposition according to claim 6, wherein the acyclic quaternaryammonium salt is selected from ditallowdimethyl ammonium methylsulfate,di(hydrogenated tallow)dimethyl ammonium methylsulfate,distearyldimethyl ammonium methylsulfate or chloride and dicocodimethylammonium methylsulfate.
 11. A composition according to claim 5 or 6, inwhich the cyclic quaternary ammonium salts are selected fromdi(hydrogenated tallow)dimethyl imidazolinium methylsulfate,1-ethylene-bis(2-tallow-1-methyl) imidazolinium methylsulfate.
 12. Acomposition according to claim 5 or 6, in which the diamido quaternaryammonium salts are selected from methyl-bis(hydrogenated tallowamidoethyl)-2-hydroxethyl ammonium methyl sulfate and methylbi(tallowamidoethyl)-2-hydroxypropyl ammonium methylsulfate.
 13. Acomposition according to claim 5 or 6, in which the biodegradablequaternary ammonium salts are selected fromN,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium methyl sulfate andN,N-di(tallowoyl-oxy-propyl)-N,N-dimethyl ammonium methyl sulfate.
 14. Acomposition according to any of the preceding claims which also containsan adjuvant selected from an emulsifier, perfume, colouring dye,opacifier, fluorescent whitening agent, bactericide, nonionicsurfactant, anti-gelling agent and corrosion inhibitor.
 15. A method forthe improvement of UPF of a textile article, comprising applying, to apreviously washed article, a fabric rinse composition comprising a) 0.1to 10% by weight of a UV absorber of formula (1), based on the totalweight of the composition; b) 5 to 25% by weight, based on the totalweight of the composition, of a fabric care ingredient; and c) theremainder being substantially water.
 16. A method for the reducing ofthe fading of fabrics from sunlight, comprising applying, to apreviously washed article, a fabric rinse composition comprising: a) 0.1to 10 by weight of a UV absorber of formula (1), based on the totalweight of the composition; b) 5 to 25%, especially from 10 to 20% byweight, based on the total weight of the composition, of a fabric careingredient; and c) the remainder being substantially water.
 17. A methodaccording to claim 15 or 16 wherein the textile article treated iscomposed of wool, polyamide, cotton, polyester, polyacrylic, silk or anymixture thereof.